Formed in situ separator for a battery

ABSTRACT

A battery including a polar solvent transportive, ionically conductive separator formed directly on an electrode is prepared by applying a coating composition containing a polymer or gel dispersed in a polar solvent directly to the electrode surface and solidifying materials in the coating composition to form a separator membrane.

FIELD OF THE INVENTION

This invention relates to batteries and in particular to separators foralkaline cells.

BACKGROUND OF THE INVENTION

Alkaline batteries are generally cylindrical in shape and include anannular cathode disposed between the outer casing of the battery or can,and the anode material which occupies a cylindrical volume having alongitudinal axis generally coincident with that of the battery and can.Located between the cathode and the anode material is a separator whichelectrically insulates the cathode from the anode material, but whichabsorbs electrolyte and allows water transport and ion transfer betweenthe electrodes. Heretofore, the separators used in alkaline batterieshave generally been limited to commercially available battery separatorpapers and cellophane films.

While conventional battery separator paper has proven satisfactory, itwould be desirable to provide methods and materials which would allowthe separator to be installed at a lower cost using a simplified processand apparatus. In particular, the equipment used to cut and place thepaper separators into the batteries are relatively complicated andexpensive. Additionally, preparing the equipment used to cut and placethe paper separators into the batteries requires sampling of the paperused to form the separators and adjustments of the equipment dependingon the particular properties of the paper being used. Another problemwith the use of paper separators is that process reliability issensitive to the internal diameter of the cathode. For example,variations in the internal diameter of the cathode along thelongitudinal length of the battery can result in areas wherein theseparator does not intimately contact the cathode. Also, changes inanode basket volume affects cell performance. As a result, theinterfacial area for ionic transport may be substantially reduced ascompared with a battery having a separator basket with an internaldiameter which does not vary along either the longitudinal or radialdirection and wherein the separator is substantially in continuouscontact along the entire internal cylindrical surface of the cathode.Another problem with paper separators is that because of the relativelycomplicated manipulations required to place the separators into thebatteries, long process cycle times are required and process capabilityis generally low and varies widely between machines and even for anyparticular machine. A still further disadvantage with paper separatorsis that the paper takes up a substantial amount of volume within thecell, which, in turn, requires a substantial amount of electrolyte towet the separator. Paper separators work optimally when wet and lessefficiently when only damp. Also, the paper does not intimately contactthe cathode over the entire cathode/separator interface, especially atthe bottom of the separator where the folds occur, creating unusedvolume within the cell. Side seams of conventional paper separators alsoconsume cell volume. A still further disadvantage with conventionalpaper separators is that the defect rate is greater than desired.

An alternative method for preparing an electrochemical cell which doesnot involve the use of a paper separator involves forming a polystyreneseparator by placing a pre-determined amount of polystyrene solutiondirectly on the surface of a cathode and removing the organic solvent,thereby leaving a substantially continuous coating on the surface of thecathode. This method is generally undesirable and impractical because ittypically requires placement of a reinforcing means on the surface ofthe cathode before application of the solution containing polystyrene,and requires evaporating large quantities of volatile organic solventssuch as methylene chloride, tetrahydrofuran, ethyl acetate, acetone,benzene, toluene, and trichloroethylene. Placing of a reinforcing meanson the surface of the cathode adds to the cost of the battery andrequires complicated automation comparable to that required forautomatically incorporating a paper separator into a battery. The use ofvolatile organic solvents is extremely undesirable due to health relatedissues (e.g., toxicity), safety related issues (e.g., flammability) aswell as the difficulty and expense involved in avoiding environmentalcontamination. Some solvents if not entirely removed can detrimentallyaffect cell performance.

SUMMARY OF THE INVENTION

The invention has as an objective the provision of an improved method ofconstructing a battery using a separator which is installed within thebattery without folding operations, and elimination of the variousproblems enumerated above relating to the use of conventional paperseparators and polystyrene separators. A further objective of thisinvention is to provide batteries having improved volumetric efficiency,improved solvent transport characteristics across the separator, andimproved ionic conductivity across the separator.

The above objectives are met, and the disadvantages with paperseparators enumerated above are overcome by a battery having a separatorformed directly on an electrode by applying a coating compositioncomprising a polymer or gel dispersed in a polar solvent to the surfaceof the electrode and solidifying materials in the applied coatingcomposition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-3 illustrate a method for forming a separator directly on acathode by applying a coating composition to the cathode surface andallowing the coating composition to solidify.

FIG. 4 illustrates an alternative apparatus for applying a coatingcomposition to a cathode surface of an alkaline battery.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention encompasses batteries having a separator which is formeddirectly on an electrode by applying a polar solvent based coatingcomposition, such as an aqueous coating composition, to the electrodesurface and allowing the coating composition to solidify. Although theinvention will be primarily described with respect to cylindricalbatteries, it is not limited to cylindrical shaped batteries, butinstead may be applied to batteries of various other shapes. Theexpression “polar solvent based coating composition” refers to acomposition which can be applied to a surface using liquid coatingtechniques, and wherein the solvent portion of the composition iscomprised mostly of polar molecules. Examples of polar solvents includewater, alcohol, and sulfuric acid. The invention hereinafter will, ingeneral, be described with respect to aqueous coating compositions, itbeing understood that other polar solvents may be employed withoutdeparting from the spirit and scope of this invention.

The method involves using any of various conventional coatingapplication techniques including, but not limited to, centrifugalcasting, spinning disk coating, spray coating, slush molding,electrostatic spraying and thermoforming. Other application techniqueswhich may be used include inverted can spray coating wherein the coatingcomposition is sprayed vertically upwardly into an inverted battery cancontaining a cathode, dip coating wherein the battery can containing thecathode is filled with the coating material and excess coating materialis subsequently poured out of the battery can, pad coating wherein anexpandable cylindrical pad is dip coated with the coating compositionand pressed against the inner surface of the cathode to transfer thecoating composition to the cathode surface, brush coating, roll coating,slot extrusion coating wherein the coating composition is applied to thecathode surface from an extrusion die, vacuum forming, blow molding, andpour-in-place gelling wherein a gel precursor is poured into the cathodeand a forming plug is thereafter inserted into the cathode followed byrapid curing, or a combination of these techniques. Presently preferredcoating application techniques include ram molding, centrifugal casting,and spray coating.

The ram molding technique for applying the coating composition to theinternal surfaces of the cathode is illustrated in FIGS. 1-3. As shownin FIG. 1, the coating composition 10 is introduced into the bottom of abattery 12 having a cathode 14. Next, as shown in FIG. 2, a forming ram16 is introduced into the cathode to cause the coating composition toflow up between the ram and the inner surface of the cathode. After thecoating composition solidifies or sets, the ram 16 is removed from thebattery 12, leaving a separator 18 which is formed directly on thecathode. In FIG. 4, there is shown an alternative forming ram 20 havingan internal conduit or bore 22 with an outlet port 24 at a lower endthereof. The forming ram 20 is first inserted into the battery 12 havinga cathode 14 as shown in FIG. 4. Thereafter, coating composition isintroduced into the bottom of the battery through conduit 22 from outletport 24. The coating composition flows through the ram, into the bottomof the battery, and up into the annulus between the ram and the innersurface of the cathode 14. The ram molding technique is believed to haveseveral potential advantages. First, the shape of the formed separator18 can be controlled by controlling the dimensions of the ram and thecathode internal diameter. Variations in temperature, viscosity, andsolids loading in the liquid coating composition can be tolerated. Thisallows refinements in the coating composition to be made withoutchanging the application process. The ram design can allow the shape ofthe separator to be tailored to improve performance characteristics. Forexample, the edges of the ram can be chamfered to decrease stress risersin the separator membrane. Also, the thickness of the membrane can bevaried at different locations. The ram geometry allows the coatingcomposition to be accurately applied over the top of the cathode shelf26, along the sides 28, and on the bottom surface of the can. The anodevolume formed by ram molding can be very accurately controlled ascompared with conventional batteries having a folded paper separator.The ram molding technique is well suited to continuous automatedproduction.

Another desirable technique for applying the coating composition to theinner surface of the cathode is centrifugal casting or spin coating.This technique involves first introducing the coating composition into acathode cup disposed in and integrally connected to a cylindrical can.Thereafter, the cathode cup and cylindrical can are rotated at a highspeed, or may already be rotating at a high speed when the material isintroduced. As the cathode rotates, the material flows up along theinternal surface of the cathode and solidifies or cures in place. Theaxis of rotation of the cylindrical can in which the cathode is disposedmay be at any angle between and including a vertical axis and ahorizontal axis. The can may be inverted such that gravitationalacceleration assists the flow of coating composition out of the can.Centrifugal casting is believed to have several advantages includingeven coating of the internal cathode surface regardless of surfaceirregularities on the cathode surface, filling of voids in the cathodesurface such as where the cathode material spalls off during cathodemolding, and the ability to provide fixed or predetermined separatormaterial volume. The centrifugal casting technique is tolerant to looseparticles of cathode material left from cathode molding. Anotheradvantage of centrifugal casting or spin coating is that the internalsurface of the separator will be very smooth.

Another desirable technique for applying the coating composition to theinternal surface of the cathode is spray coating. With this technique,the liquid separator coating composition is sprayed onto the surface ofthe cathode and solidifies or cures in place. A major advantage of thespray coating process is its mechanical simplicity.

The aqueous separator coating composition may be an aqueous solution,gel, dispersion, slurry, or combination thereof which can be applied inliquid form using liquid coating application techniques, and which willsolidify to form a separator directly on the cathode surface.Solidification of the coating composition refers to any process ofdrying, curing, gelling, cross-linking, polymerization, freezing (i.e.,thermal solidification), or combination thereof which results in astable electrically insulating barrier which will allow ionic transportbetween the electrodes and will adhere to the cathode during theproduction and useful life of a battery. The solidified coating ispreferably less than 0.020 inches thick, more preferably less than0.005, with thinner coatings being desirable to maximize anode basketvolume. The separator coating compositions preferably smooth out or fillany surface irregularities in the cathode surface and preferably havecontrollable thickness, including uniform and variable thickness.

An advantage with the formed in situ separators is that they are inintimate and complete contact with the electrode surface on which theyare formed, i.e., the separator is in substantially continuous contactwith the surface of the electrode upon which the separator is formed.This differs significantly from paper separators which normally havesignificant areas which are not in contact with adjacent electrodesurfaces. The improved contact provided by the in situ formed separatorsprovides enhanced ion transport properties and improved cellperformance. The formed in situ separators can be made thinner thanpaper separators and can therefore occupy less space than a paperseparator, thereby allowing more space in a battery for electrodematerial, and hence enabling improved battery performance. For example,the formed in situ separators may be employed to provide batteries inwhich the separator occupies less than 10% of the cell volume.

The solidified or cured separators should be mechanically tough,resistant to mechanical shock and not easily ruptured or damaged oncecured. The resulting separator should also exhibit sufficient tearresistance to prevent tears across gaps between the cathode rings,cathode-to-can interfaces, or the surfaces of the anode. The separatorcoating composition should also solidify or cure to form a separatormembrane having sufficient elasticity to sustain at least 25% expansionof the cathode dimensions during discharge without tearing or separatingfrom the electrode. The separator should also exhibit sufficientpenetration resistance to resist penetration by zinc dendrites andshould not provide a path for formation of zinc dendrites as do paperseparators. The compression strength of the separator should besufficient to prevent squeeze-out of liquid under full compressionbetween a discharged anode and cathode. The separator should retainefficient mechanical properties throughout the operating temperaturerange of −20° C. to 71° C., but also −40° C. to 85° C. abusetemperatures. The separator should also exhibit high retentiveness ofelectrolyte solution, even under compression and when either the anodeor cathode are dried out, i.e., the separator should be the lastcomponent to dry out during cell discharge. The separator must remaindimensionally stable in the presence of 45% potassium hydroxide, andshould not swell or shrink in the presence of water or potassiumhydroxide and retain mechanical integrity. Further, the separatorsshould preferably adhere to ring molded, and impact molded electrodes.The separators should also preferably adhere to rod-shaped, ring-shaped,strip-shaped, washer-shaped, and other shaped electrode surfaces. Inaddition to the above mechanical requirements, the separator shouldexhibit certain electrical properties. First, the separator should notbe electrically conductive, i.e., it should act as an electricalinsulator between the anode and cathode. The separator should maintainthe electrical insulating characteristics over the projected life of thebattery, which is at least about 5 years. The separator should alsoexhibit high ionic conductivity which meets or exceeds the hydroxyl ionflux density of the anode at the anode/separator interface, and whichmeets or exceeds the hydroxyl ion flux density of the cathode at thecathode/separator interface, i.e., the separator should not be ratelimiting. The separator should also have surface-to-surface ionconducting pathways, even in partially dehydrated condition. Theseparator should also exhibit certain chemical properties. First, theseparator must be chemically stable or inert (i.e., must not decompose)in a 45% potassium hydroxide solution. The separator should also exhibitchemical stability under a potential difference of up to 2 volts. Theseparator should also exhibit high gas permeability. In order to preventlocal conditions favorable to zinc oxide precipitation, the separatorshould exhibit good shorting resistance. The separator must not causecorrosion of nickel plated steel at the cathode potential, and shouldexhibit minimum permanent bonding of electrolyte and water. Theseparator should also be resistant to catalytic decomposition by themetals used in the construction of the battery.

Water and ionic transport properties are also an importantconsideration. Water should readily diffuse through the separator sothat small concentration gradients will result in high diffusion rates.Poor diffusion would result in cell polarization under heavy drain. Theseparator must pass hydroxyl ions from cathode to anode and must passpotassium ions from anode to cathode. The pathway for ion transportshould be somewhat tortuous. A suitable transference number of hydroxylion in potassium hydroxide is 0.73. The hydration number of potassiumion should be from about 1 to about 2. The separator should act as abarrier to prevent movement of electrode materials from the cathode toanode and from the anode to the cathode. Desirably, the coatingcompositions should offer the ability to tailor the transportcharacteristics.

The coating compositions of this invention may solidify or freeze toform an aqueous gel separator having a solvent content greater than 90%by weight. This high solvent content allows the separator to behave asan electrolyte reservoir.

It is believed that a wide variety of aqueous gels, and polymerdispersions can be formulated to achieve the desired separatorcharacteristics. Examples of coating compositions which have been foundto be suitable for forming a separator directly on the surface of acathode include seamless gels comprising kappa-carrageenan, hydroxyethylcellulose, and a blend of kappa-carrageenan and hydroxyethyl cellulose.Other suitable compositions may include lambda- or iota-carrageenan,other hydroxyalkyl celluloses such as hydroxymethyl- and/orhydroxypropyl cellulose, and combinations thereof. For example,kappa-carrageenan forms a strong film when cast as a 2-5 weight percentfilm with water. Hydroxyethyl cellulose cross-linked with vinyl sulfoneforms a strong gel with very high ionic conductivity. However,separators formed from kappa-carrageenan alone are not as strong aswould be desired, and separators cast from hydroxyethyl cellulose aloneexhibit shrinkage which is generally more than would be desired for AAAand larger size cells, but is acceptable for smaller cells. Othercoating compositions which may be employed include aqueous compositionscontaining polyvinylpyrrolidone, such as compositions comprised ofcarrageenan (e.g., kappa-, lambda-, and/or iota-carrageenan) andpolyvinylpyrrolidone.

It has been discovered that separator coating compositions containing ablend of kappa-carrageenan and hydroxyethyl cellulose are capable offorming separators exhibiting very high ionic conductivity withexceptional strength and shrinkage characteristics. Thus, a blend of twodifferent polymers may be employed to provide a composition which can beused to form in situ separators having an outstanding combination ofproperties.

Kappa-carrageenan is a naturally occurring marine colloid. Morespecifically, kappa-carrageenan is a sulfur phycocolloid (apolysaccharide) occurring in algae. A major potential advantage ofkappa-carrageenan as a separator is that it is a low-temperaturethermoformable thermoplastic gel, preferably having a melting pointgreater than 71° C. Other potential advantages are that it is non-toxic,water-soluble, very low in cost, and readily available commercially. Theseparators may be cast from a coating composition containingapproximately 1 to 10 percent, and more desirably 2 to 5 percent, byweight of the composition. However, higher and lower concentrations maybe used.

Hydroxyethyl cellulose is a non-ionic, water-soluble, cellulose ether.The potential advantages of hydroxyethyl cellulose as a batteryseparator material are that it is water-soluble, low cost, commerciallyavailable, can be chemically cross-linked (with divinylsulfone, forexample) and is compatible with other aqueous based polymers. A suitableseparator coating composition which can be used to form a batteryseparator may be prepared as a 5 weight percent mixture of hydroxyethylcellulose in water, although higher and lower concentrations may also beused. Divinylsulfone cross-linking agent is desirably added to thecoating composition in an amount of from about 0.05 to about 2% of theweight of the hydroxyethyl cellulose, and more desirably from about 0.10to about 1 weight percent. In general, higher amounts of cross-linkingagent provide separators which exhibit higher electrical resistance andgreater strength at the expense of ionic conductivity.

Another material which has been found suitable for preparing a separatordirectly on a cathode surface is cellulose viscose. Cellulose viscose isa viscous liquid consisting of concentrated aqueous alkali containing asolution of cellulose/xanthate complex. It can be coagulated in dilute(e.g., 10%) sulfuric acid to form regenerated cellulose. The potentialadvantages of cellulose viscose are that it is water-soluble, low cost,stable to concentrated alkali, and has an existing performance record inalkaline batteries. Separators can be cast from solutions containingabout 5 weight percent cellulose/xanthate complex, although higher andlower concentrations may also be used.

Examples of other materials which can be used in the preparation of thecoating compositions which are applied to the cathode to form aseparator include various synthetic polymers prepared as aqueousdispersions. Examples include aqueous dispersions of cellulose,polyurethane, acrylic polymers, polyvinyl acetate, and epoxy polymers;and dispersions of cellulose in polar organic solvents such as N-methylmorpholine oxide.

The coating compositions may and often desirably contain fibers, such aswood pulp, polyolefin, cellulose, cotton, rayon, boron, boron carbide,boron nitride, carbon, aluminum silicate, and/or fused silica fibers.Polyolefin fibers include halogenated polyolefin fibers, such as thoseprepared from fluorinated polypropylene. The amount of fiber in thecomposition is desirably from about 3% to about 50%, and more preferablyfrom about 3% to about 20%, of the weight of the polymer or gel materialin the composition. Fibers are included to provide physical barrierintegrity, and to reinforce and structurally strengthen the separator.

Particularly preferred coating compositions are those comprisingkappa-carrageenan, hydroxyethyl cellulose, and cellulose fibers. Thehydroxyethyl cellulose, kappa-carrageenan, and cellulose fibers arepreferably dispersed in water to form the separator coating composition.The weight ratio of hydroxyethyl cellulose to kappa-carrageenan ispreferably from about 1:3 to 3:1, and more preferably from about 1:1 toabout 3:1, although higher and lower ratios may also be used. The amountof hydroxyethyl cellulose and kappa-carrageenan in the coatingcomposition may vary considerably, but is generally from about 1% toabout 10% by weight, although higher and lower concentrations may alsobe used. Cross-linking agents such as divinylsulfone may be employed inamounts up to about 2% of the weight of the composition. Anothersuitable cross-liking agent which may be employed is trishydroxy methylcyanurate, which is commercially available from American Cyanamide andsold under the trademark CYMEL®. The coating compositions preferablyhave a solvent content greater than 50% by weight during application.

The invention will now be described with reference to the followingnon-limiting examples.

EXAMPLES Fabrication of Functional Batteries

Three master batches of separator coating compositions were prepared.The first coating composition contained 5% by weight kappa-carrageenanin water. The second coating composition contained 5 weight percenthydroxyethyl cellulose in water with 1 weight percent potassiumhydroxide. The third coating composition was a 3:1 mixture of thekappa-carrageenan master batch to the hydroxyethyl cellulose masterbatch. The kappa-carrageenan and kappa-carrageenan hydroxyethylcellulose blends were heated above 90° C. to melt the kappa-carrageenanand were held between 90° C. and 100° C. in a double boiler. A stainlesssteel ram was fabricated that was 40 mils smaller in diameter than theinside diameter of a D cell cathode. The ram or mandrel was mounted in acollect on a vertical milling machine. A V-block was positioned on amachine table such that when a D cell was clamped in the V-block thecenter line of the ram was in line with the center of the cell. Aspindle stop on the machine was set so that the ram would stopapproximately {fraction (1/16)} inch above the bottom of the can. Withthis configuration, the formed separator was to be 0.020 inches thick onthe cathode surface and 0.062 inches thick on the bottom. The separatorcould actually be significantly thinner than this. However, during thedevelopmental work it was preferable to have a thicker separator thanneeded to compensate for any tooling inaccuracies, cathode particleentrapment, bubbles in the liquid separator, etc. Separators were formedfrom the kappa-carrageenan coating composition and from thekappa-carrageenan/hydroxyethyl cellulose blend in the cells by fillingthe cells to the top with the liquid separator coating composition andlowering the ram into the cathode. As the ram entered the cathode,excess liquid flowed out. After the separator material cured orsolidified, the ram was removed. In the case of the hydroxyethylcellulose formulation, vinyl sulfone cross-linker was added and mixedprior to pouring the material into the cathodes. The filling and ramforming process was performed twice on each cell in order to fill anyvoids that might be caused by air bubbles, uneven separator materialflow, etc. Anode paste was added to fill the cells to the top of thecathode and collector assemblies were placed on the cells.

Nine cells were formed with the kappa-carrageenan separator material.All of the cells had an initial voltage of from 1.51 to 1.64 volts.Seven functional cells were put on 71° C. shelf-life testing. Two of thecells had OCV above 1.2 after storage for 5 weeks at 71° C.

Four cells were made using the kappa-carrageenan/hydroxyethyl celluloseblend. Two of the cells had an initial voltage above 1.5. The other twocells have voltages below 1.2.

Based on these tests, it was determined that battery separator membranesmade from kappa-carrageenan coating compositions andkappa-carrageenan/hydroxyethyl cellulose coating compositions can beused in alkaline cells. These tests also demonstrated that the rammolding process for forming the separator membranes is workable.

Fabrication of AA Batteries

AA alkaline batteries were prepared as follows. A 5 weight percentsolution of kappa-carrageenan in water was prepared. Thekappa-carrageenan solution was held at 90° C. in a hot water bath. Alarge syringe with a hypodermic needle was filled with thekappa-carrageenan solution. The kappa-carrageenan coating compositionwas introduced to the bottom of the AA can containing the cathode. Thecan containing the cathode was filled to the top with thekappa-carrageenan coating composition. This eliminated the need foraccurately metering the kappa-carrageenan. During the molding processthe excess was allowed to flow over the top of the can. Immediatelyafter the kappa-carrageenan was introduced, the molding ram was loweredinto the cathode and the kappa-carrageenan coating composition flowedbetween the outer surface of the ram and the inner surface of thecathode. After the coating composition solidified, the ram was raised,and the cathode was removed from the ram. Excess kappa-carrageenanmaterial was removed from the area above the cathode shelf. Anode pastewas introduced into the cathode having the separator formed directlythereon, and a collector assembly was placed on the can and pressed inplace using a small hand press. The cells were tested for open circuitvoltage immediately after fabrication and for a short period thereafter.The cells were put on 71° C. shelf-testing and 71° C., 0.8 voltspost-partial discharge (PPD) testing. Controls were made by adding anodepaste to cathodes lined with conventional paper separators and bypressing collector assemblies in place.

One hundred three (103) operational cells were made withkappa-carrageenan separators. All of the kappa-carrageenan separatorswere fabricated using the ram molding technique. These tests proved thatoperational batteries could be fabricated with separator membranes thatare made by applying a coating composition to the cathode surface andallowing the coating composition to solidify.

Fabrication of Alkaline Cells Having Kappa-Carrageenan/HydroxyethylCellulose Blend Separators

Two master batches were prepared, including a first containing 5%kappa-carrageenan in water, and a second containing 5% hydroxyethylcellulose in water (both on a weight basis). The pH of the hydroxyethylcellulose batch was increased to 12 by addition of solid potassiumhydroxide. The batches were mixed in a ratio of three parts of thecomposition containing the kappa-carrageenan to one part of thecomposition containing the hydroxyethyl cellulose. The AA batteries wereprepared in accordance with the method described above. Sixty (60)operational cells were made with the kappa-carrageenan/hydroxyethylcellulose blend separators, and 50 controls were made with conventionalpaper separators. The open circuit voltages for the batteries containingthe kappa-carrageenan/hydroxyethyl cellulose separators were comparableto conventional batteries containing a paper separator. Three (3) of thecells containing the ram molded kappa-carrageenan/hydroxyethyl celluloseseparators lasted 8 weeks with a final average open-circuit voltagereading of 1.236 volts. The remainder of the cells failed after 2 to 3weeks. These results demonstrate that alkaline batteries can besuccessfully prepared with a separator which is formed by applying acoating composition to the cathode surface and allowing the coatingcomposition to solidify.

Centrifugally Cast Separators

A kappa-carrageenan/hydroxyethyl cellulose blend as described above wassuccessfully centrifugally cast on the inner surface of a cathode for acylindrical AA alkaline cell. The AA cells were inserted into a supportfixture that was mounted to the output shaft of a DC motor and rotatedat approximately 20° to horizontal. The axis of rotation was coincidentwith the longitudinal axis of the cylindrical cell. The coatingcomposition containing kappa-carrageenan and hydroxyethyl cellulose wasintroduced into the cathode using a syringe as previously described. Thecell was then rapidly accelerated to 2500 rpm and held at that speed forapproximately 2 minutes, causing the liquid to flow up the sides of thecathode and to solidify or set-up. In order to avoid complications ofmeasuring the amount of liquid injected into the cell, the cells wereoverfilled. During the spinning operation, the excess liquid exited fromthe top of the cell. After the separators set-up, the cathodes wereremoved from the spinning fixtures, and additional potassium hydroxidewas added. The anode paste was then added along with additionalpotassium hydroxide, and the collector was installed. Eleven (11)operational cells were produced by the centrifugal casting technique.This test demonstrated that centrifugal casting can be effectively usedfor applying a coating composition to a cathode surface to form aseparator directly on the cathode surface.

Polyvinyl Acetate Separators

The above centrifugal casting process was repeated using a polyvinylacetate aqueous dispersion. Three (3) operational cells were made withpolyvinyl acetate membranes.

Fabrication Of Cells Using Separator Coating Composition ContainingSolid Cellulose Fibers

A master batch of 5% kappa-carrageenan (weight basis) in water wasprepared at 90° C. A master batch of 5% hydroxyethyl cellulose (byweight) in 1% potassium hydroxide (by weight) was prepared. Thekappa-carrageenan composition and the hydroxyethyl cellulose compositionwere mixed in a 3:1 ratio at 90° C. To this blend was added 15%cellulose fiber by weight. Ram molding, as described above, was used forpreparing AA cells having a separator formed from the coatingcomposition containing kappa-carrageenan/hydroxyethylcellulose/cellulose fiber. Seventy-seven (77) operational cells wereprepared with the kappa-carrageenan/hydroxyethyl cellulose/cellulosefiber blend. Nine or ten batteries subjected to a 71° C. shelf test wereoperational after 8 weeks, and four of five batteries subjected to a 0.8volt PPD teste were operational.

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments shown in the drawings and describedabove are merely for illustrative purposes and not intended to limit thescope of the invention, which is defined by the following claims asinterpreted according to the principles of patent law, including thedoctrine of equivalents.

What is claimed is:
 1. A battery comprising: first and secondelectrodes; an alkaline electrolyte; and and an ionically conductiveseparator disposed between the electrodes, said separator formed byapplying a coating composition to the surface of at least one of theelectrodes and solidifying material contained in the coatingcomposition, said coating composition comprising a polar solvent,kappa-carrageenan, hydroxyethyl cellulose, divinylsulfone cross-linkingagent and fiber, wherein the weight ratio of hydroxyethyl cellulose tokappa-carrageenan is from about 1:3 to about 3:1, the amount ofcross-linking agent is from about 0.05 to about 2% of the weight of thecomposition, the amount of hydroxyethyl cellulose and kappa-carrageenanis from about 1% to about 10% by weight of the composition, and theamount of fiber is from about 3% to about 50% of the weight of thecomposition.
 2. A method of providing a separator on an electrode for analkaline battery, comprising: introducing a coating composition into thebottom of the electrode; introducing a forming ram into the electrode toform an annular space between the interior surface of the electrode andthe outer surface of the ram thereby causing the coating composition toflow up into said annular space; solidifying the coating composition onsaid electrode surface to form a separator membrane; and removing theram from the electrode.
 3. A method of providing a separator on anelectrode surface for an alkaline battery, comprising: introducing a ramhaving a coating composition outlet port into the electrode; introducinga coating composition into the electrode through the outlet port therebycausing the coating composition to flow into an annular space betweenthe ram and the inner surface of the electrode; solidifying the coatingcomposition on the electrode's surface to form a separator membrane; andremoving the ram from the electrode.
 4. A method of providing aseparator on an electrode for an alkaline battery, comprising: applyinga liquid aqueous coating composition to an electrode surface, whereinthe coating composition comprises cellulose viscose; and solidifying thecoating composition on said electrode surface to form a separatormembrane.
 5. A method of providing a separator on an electrode for analkaline battery, comprising: applying a liquid aqueous coatingcomposition to an electrode surface, wherein the coating compositioncomprises cellulose viscose and fibers, said fibers selected from thegroup consisting of cellulose, cotton, rayon, boron, boron carbide,boron nitride, aluminum silicate, fused silica fibers, wood pulp andpolyolefin fibers; and solidifying the coating composition on saidelectrode surface to form a separator membrane.